The present invention relates to a simple process for the industrial preparation of silyl-bridged fluorenyl-cyclopentadienyl ligands and also to a process for preparing silyl-bridged fluorenyl-cyclopentadienyl metallocenes.
The metallocenes of transition group IV of the Periodic Table, i.e. the metallocenes of titanium, zirconium and hafnium, have in recent years proven to be an important consitutent of a significant new class of polyolefin catalysts (H.-H. Brintzinger, D. Fischer, R. Mxc3xclhaupt, B. Rieger and R. Waymouth, Angew. Chem. Int. Ed. Engl., 34 (1995) 1143; M. Aulbach and F. Kxc3xcber, Chiuz, 28 (1994) 197). The metallocenes are, if appropriate in combination with one or more cocatalysts, used as catalyst component for the polymerization and copolymerization of olefins. Bridged metallocenes, known as ansa metallocenes, play an important role in, for example, the stereoselective preparation of polypropylene. Thus, for example, syndiotactic polypropylene can be prepared using bridged fluorenyl-cyclopentadienyl metallocenes (J. A. Ewen, R. L. Jones and A. Razavi, J. Am. Chem. Soc., 110 (1988) 6255).
The synthesis of silicon-bridged fluorenyl-cyclopentadienyl metallocenes and the use of these compounds in the polymerization of olefins is known (K. Patsidis, H. G. Alt, W. Milius and S. J. Palackal, J. Organomet. Chem., 509 (1996) 63-71; W. Spaleck, M. Aulbach, B. Bachmann, F. Kuber and A. Winter, Macromol. Symp. 89 (1995) 237-247; U.S. Pat. No. 5401817; U.S. Pat No. 5393911; EP 0628577). The synthesis of the silicon-bridged fluorenyl-cyclopentadienyl metallocenes is carried out as shown in the scheme below using a zirconocene as an example: 
where R1, R2 are identical or different alkyl or aryl radicals and M can be Li, Na, MgCl or MgBr and Cp is cyclopentadiene.
A disadvantage of the syntheses described in the literature with regard to transfer to the production scale is the use of critical solvents such as diethyl ether (highly flammable) or hexamethylphosphoramide (carcinogenic). Furthermore, the isolation of fluorenyl lithium or the isolation of the dilithium salt of the silyl-bridged fluorenyl-cyclopentadienyl ligand is a complicated step in process engineering terms.
Chromatographic purification of intermediates is also a great disadvantage on the industrial scale.
It is an object of the present invention to find methods for steps 1 to 3 in Scheme 1 which avoid the abovementioned disadvantages and can be carried out without problems under industrial conditions.
We have found that this object is achieved by carrying out steps 1-3 of the above scheme (Scheme 1) using particular solvents or solvent mixtures and a particular reaction methodology, thus enabling the steps to be carried out under conditions which are feasible in process engineering terms and are acceptable in terms of safety.
The present invention accordingly provides a process for preparing compounds of the formula (IV) 
wherein
R1, R2 are identical or different C1-C20-hydrocarbon radicals, preferably C1-C10-alkyl or C6-C14-aryl radicals, particularly preferably methyl, ethyl, tert-butyl or phenyl,
R3, R4, R5, R6, R7, R8, R9, R10 are identical or different and are each hydrogen, halogen or a C1-C20-hydrocarbon radical, preferably hydrogen, C1-C10-alkyl, C1-C10-alkenyl, C6-C14-aryl, C7-C12-alkylaryl or C7-C12-arylalkyl, particularly preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, amyl, hexyl, heptyl, octyl or phenyl, where preferably at least R4, R7, R9 and R10 are hydrogen,
R11, R12, R13, R14 are identical or different and are each hydrogen or a C1-C20-hydrocarbon radical, preferably hydrogen, C1-C10-alkyl, C1-C10-alkenyl, C6-Cl14-aryl, C7-C12-alkylaryl or C7-C19-arylalkyl, particularly preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, trimethylsilyl, triphenyl-methyl, 2-methyl-2-phenylpropyl, 2,2-diphenylpropyl, 2,2-diphenylethyl or phenyl, where preferably at least two of the radicals R11, R12, R13 and R14 are hydrogen and
L is zirconium, hafnium or titanium,
comprising the measures:
a) deprotonation of the compound of the formula (I) 
using a base,
b) reaction of the deprotonated compound from step a) with R1R2SiCl2 to give the compound of the formula (II) 
where R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined above,
c) reaction of the compound of the formula (II) obtained as described in step b) with
M+Cpxe2x88x92 to form the compound of the formula (III) 
where R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are as defined above,
M is Li, Na, K, MgCl or MgBr and
Cp is a substituted or unsubstituted cyclopentadienyl radical,
d) reaction of the compound of the formula (III) with a base and addition of LCl4, where L is zirconium, titanium or hafnium, to form the compound of the formula (IV),
wherein
i. the deprotonation of step a) is carried out in a mixture of one or more aromatic, aliphatic hydrocarbons and xcex1,xcex2-dialkoxyalkanes or xcex1,xcex2-dialkoxyaromatics,
ii. an alkane is added after deprotonation is complete and before the reaction with the organochlorosilane as described in step b),
iii.the reaction of step d) is carried out in a mixture of one or more aromatic, aliphatic hydrocarbons and a polar aprotic solvent, with the exception of diethyl ether.
In step a), the compound of the formula (I), for example fluorene, is deprotonated in an inert solvent mixture by means of a strong base, for example butyllithium, and the metal salt formed is subsequently, after addition of an alkane having from 5 to 30 carbon atoms, reacted directly without further isolation with a silicon dichloride reagent R1R2SiCl2 to give the compound (II), with the compound (II) preferably being added to the metal salt (single-vessel process).
As fluorenyl compound of the formula (I), it is possible to use unsubstituted fluorene itself or monosubstituted and polysubstituted fluorenes, as described, for example, in EP 0528 287 A. Examples are 1-methylfluorene, 4-methylfluorene, 1-tert-butylfluorene, 2-ethylfluorene, 2-tert-butylfluorene, 4-tert-butylfluorene, 4-phenylfluorene, 2,7-di-tert-butyl-fluorene, 2,7-di-tert-butyl-4-methylfluorene and 2,7-di-tert-butyl-4-phenylfluorene. Furthermore, instead of substituted fluorenes, it is also possible to use the fluorene-analogous heteroatom-substituted tricyclic compounds described in WO 98/22486. Preference is given to using fluorene, 4-methyl-fluorene, 2-tert-butylfluorene, 4-tert-butylfluorene, 4-phenyl-fluorene and 2,7-di-tert-butylfluorene; very particularly preferably unsubstituted fluorene and 2,7-di-tert-butylfluorene.
In the deprotonation of step a), use is made of an inert solvent mixture of one or more hydrocarbons and one or more xcex1,xcex2-dialkoxyalkanes or xcex1,xcex2-dialkoxyaromatics.
In the process of the present invention, up to one mol of xcex1,xcex2-dialkoxyalkanes or xcex1,xcex2-dialkoxyaromatics is added per mol of fluorene, preferably less than half a mol.
The xcex1,xcex2-dialkoxyalkanes or xcex1,xcex2-dialkoxyaromatics used according to the present invention are preferably 1,2-dimethoxyethane (DME), 2,3-dimethoxybutane, 1,2-diethoxyethane, dioxane, diethylene glycol dimethyl ether, 1,2-dimethoxybenzene, 1,2-diethoxybenzene and 2-ethoxyanisole, in particular 1,2-dimethoxyethane (DME).
The hydrocarbons are aromatic and aliphatic hydrocarbons such as pentane, hexane and its isomers, heptane, (copyright)Exxsol DSP 100-120, toluene, ethylbenzene, xylene or tetrahydronaphthalene, preferably toluene and heptane.
To suppress the formation of silyl-bridged bisfluorenylene, the silicon dichloride reagent R1R2SiCl2 is used in excess over the metal fluorenyl salt, with the molar ratio being from 1.1:1.0 to 3.5:1, preferably from 1.25:1 to 2.5:1. The excess silicon reagent can be removed, for example by distillation or by crystallization, before addition of the M+Cpxe2x88x92.
The deprotonation of the compound of the formula (I), namely the fluorene, is carried out in a temperature range from xe2x88x9230xc2x0 C. to 80xc2x0 C., preferably from 20xc2x0 C. to 60xc2x0 C., and the subsequent reaction with the silicon reagent to form the compound of the formula (II) is carried out in a temperature range from xe2x88x9278xc2x0 C. to 50xc2x0 C., preferably from xe2x88x9230xc2x0 C. to 30xc2x0 C.
The fluorenyl-monochloro-silicon compound of the formula (II) is obtained after reaction with R1R2SiCl2 and subsequent removal of the solvents and of excess silicon dichloride reagent R1R2SiCl2 (step b). The possible removal of the metal chloride, for example lithium chloride, is preferably carried out prior to the removal of the solvents. The pure compound of the formula (II) can be obtained by crystallization from a hydrocarbon, preferably toluene and/or heptane.
In step c), a solution of a substituted or unsubstituted alkali metal or alkaline earth metal cyclopentadienide M+Cpxe2x88x92 in a cyclic or acyclic ether or polyether, with the exception of diethyl ether, is reacted with the fluorenyl-monochloro-silicon compound of the formula (II) to give the compound of the formula (III). Substituted or unsubstituted cyclopentadienes CpH can be reacted with strong bases such as sodium, potassium, sodium hydride, potassium hydride, dibutyl magnesium, butyloctylmagnesium, Grignard compounds, methyllithium or n-butyllithium to give the compounds M+Cpxe2x88x92. Examples of preferred substituted cyclopentadienes are methylcyclopentadiene, ethylcyclopentadiene, isopropylcyclopentadiene, tert-butylcyclopentadiene, n-butylcyclopentadiene, 1,3-n-butylmethylcyclopentadiene, 1,3-tert-butylmethylcyclopentadiene, 1,2-tert-butylmethylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,3-di-tert-butylcyclopentadiene and trimethylsilylcyclopentadiene.
As alkali metal or alkaline earth metal cyclopentadienide, preference is given to using sodium cyclopentadienide, which is commercially available as a solution in tetrahydrofuran (THF).
Cyclic or acyclic ethers or polyethers for the purposes of the present invention are, for example, tetrahydrofuran (THF), 2,5-dimethyltetrahydrofuran, methyl tert-butyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether. Preference is given to using THF and DME, particularly preferably THF.
When R1, R2 are phenyl, it is indicated in the literature (J. Organomet. Chem., 509 (1996) 64 or U.S. Pat. No. 5,393,911, column 15, lines 62, 63) that the 2nd reaction step does not function in THF. However, in agreement with W. Spaleck, M. Aulbach, B. Bachmann, F. Kxc3xcber and A. Winter, Macromol. Symp. 89 (1995) 237-247, it was able to be shown that when R1, R2 are phenyl, the reaction functions in THF, but the chromatographic purification described in the literature can be avoided if the process is designed appropriately.
The molar ratio of fluorenyl-monochloro-silicon compound of the formula (II) to the cyclopentadienyl anion is from 1:1 to 1:3, preferably from 1:1.5 to 1:2.5.
The reaction is carried out in the temperature range from xe2x88x9230xc2x0 C. to 65xc2x0 C., preferably from 0xc2x0 C. to 40xc2x0 C.
The product of the formula (III) is obtained after aqueous work-up and after removal of excess cyclopentadiene. For the further reaction, either the crude product (III) is used or (III) is crystallized from a suitable solvent or solvent mixture, for example toluene and/or heptane.
In the subsequent step d), the cyclopentadienylfluorenylsilane (III), namely the ligand system, is doubly deprotonated in an inert solvent mixture comprising a hydrocarbon or hydrocarbon mixture and a polar aprotic solvent using a strong base, for example butyllithium, and the resulting dilithium salt of the ligand system is reacted directly, without isolation, with a titanium tetrahalide, zirconium tetrahalide or hafnium tetrahalide source to give the metallocene (IV).
The polar aprotic solvent is a cyclic or acyclic ether or polyether, with the exception of diethyl ether, or else a tertiary amine or diamine such as tetramethylethylenediamine (TMEDA). Preference is given to using 1,2-dimethoxyethane (DME) or tetrahydrofuran (THF). P referred solvent mixtures for preparing the dilithium salt are toluene/DME and toluene/THF, particularly preferably toluene/THF.
The ratio of strong base to ligand is from 2.0:1 to 2.5:1, preferably from 2.0:1 to 2.2:1.
The ratio of the polar aprotic solvent and the strong base butyllithium is from 0.1:1 to 4:1, preferably from 0.25:1 to 2:1.
The doubly deprotonated ligand (III) is reacted with a titanium tetrahalide, zirconium tetrahalide or hafnium tetrahalide source at from xe2x88x9230xc2x0 C. to 60xc2x0 C., preferably from 0xc2x0 C. to 40xc2x0 C., to give the metallocene (IV).
As titanium tetrahalide, zirconium tetrahalide or hafnium tetrahalide source, preference is given to using the pure tetrachlorides or corresponding adducts of the tetrachlorides with donor solvents such as ethers or amines. Examples of adducts of the tetrahalides are: ZrCl4*2THF, ZrCl4*DME, ZrCl4*TMEDA, TiCl4*2THF, TiCl4*DME, TiCl4*TMEDA, HfCl4*2THF, HfCl4*2THF, HfCl4*2THF.
Particular preference is given to the abovementioned compounds of zirconium.
The isolation and purification of the metallocene (IV) is carried out by methods known from the literature (for example: J. Organomet. Chem., 509 (1996) 63-71).
Scheme 2 below once more illustrates the individual steps of the novel process for preparing metallocenes of the formula (IV) in a preferred embodiment. 
In this scheme,
R1, R2 are identical or different C1-C20-hydrocarbon radicals, preferably C1-C10-alkyl or C6-C14-aryl radicals and
R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 are identical or different and are each hydrogen, halogen or a C1-C20-hydro-carbon radical, preferably hydrogen, C1-C10-alkyl, C1-C10-alkenyl, C6-C14-aryl, C7-C12-alkylaryl or C7-C19-arylalkyl.
Preferably, R1, R2 are identical or different and are each a methyl, ethyl, tert-butyl or phenyl group, and
R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 are identical or different and are each hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, trimethylsilyl, triphenylmethyl, 2-methyl-2-phenylpropyl, 2,2-diphenylpropyl, 2,2-diphenylethyl or phenyl.
Very particularly preferably, R1 is identical to R2 and both are methyl or phenyl, R3, R5, R6, R8 are identical or different and are each hydrogen, methyl, phenyl or tert-butyl, R4, R7, R9 and R10 are hydrogen and R11, R12, R13 and R14 are identical or different and are each hydrogen, methyl or tert-butyl, where at least two of the radicals R11, R12, R13 and R14 are hydrogen.
The process of the present invention enables the target compound of the formula (IV) to be obtained industrially. The process of the present invention can be interrupted after any step and the intermediate can be isolated. This leads, in particular, to the process being able, for example, to be interrupted after step 2 in Scheme 2 and the compound of the formula (III) to be used as a stock compound. This process is likewise subject-matter of the invention.